TW201041652A - Methods for enhancing the efficiency of rhenium-promoted epoxidation catalysts and epoxidation methods utilizing these - Google Patents

Abstract

A method for enhancing the efficiency of a rhenium-promoted epoxidation catalyst is provided. Advantageously, the method may be carried out in situ, i.e., within the epoxidation process, and in fact, may be carried out during production of the desired epoxide. As such, a method for the epoxidation of alkylenes incorporating the efficiency-enhancing method is also provided, as is a method for using the alkylene oxides so produced for the production of 1,2-diols, 1,2-carbonates, 1,2-diol ethers, or alkanolamines.

Description

201041652 VI. Description of the invention: [Technical field to which the invention pertains] This document provides methods for improving the efficiency of epoxidation catalysts. Advantageously, this can be incorporated into the epoxidation process to be sustainable during both hands and therefore an epoxidation process using a fortified catalyst. [Prior Art] Catalysts are an important component of many chemical processes and are typically used to accelerate the rate of the reaction and/or increase the selectivity or efficiency of the product. When used in combination with many reactions, the catalysts have been found to be particularly advantageous for use in epoxy resins, a process that has significant industrial importance in the bulk chemical business. In the epoxidation reaction, a feed containing at least an olefin and oxygen is contacted with a catalyst to cause formation of a corresponding olefin oxide. One example of a epoxidation of a dilute hydrocarbon of a particular industrial importance is a mixture of epoxidized olefinic hydrocarbons or olefinic hydrocarbons, and this epoxidation reaction is particularly dependent on a high performance catalyst to be industrially feasible. The catalyst for the olefin furnace ring catalyst comprises a catalytic material deposited on a suitable support (carrier) either alone or in combination with one or more promoters. Those skilled in the art have been actively seeking improvements in the efficiency and/or activity of epoxidation catalysts for some time, because on the Wei (4), even a small (for example, 1%) selectivity increase can be substantially reduced. Operating costs associated with the epoxidation process. The scope of research in this field is broad, and in the field of catalyst components (such as carriers, promoters and catalytic materials), catalyst manufacturing methods and even the epoxidation process itself, it is sought to improve the efficiency of the catalyst and / or extend 201041652 The use of π life improvement. However, it is often the case that adjusting one or more of these fields can result in improvements in catalyst efficiency, activity or longevity while at the same time causing the other to decay. Alternatively, any conditions required for such conditioning may not be produced during the epoxidation process, or if epoxidation is "(iv), the production of the epoxidized product may be slowed or completely stopped. Ideally, it will be provided to improve The method of efficiency and/or activity of such epoxidation catalysts. If any of the four methods can provide Ο 催化剂 催化剂 Ο Ο Ο Ο Ο Ο 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且Any such method is particularly advantageous on site, and/or in the use of cyclization; primary, ..., utilization. SUMMARY OF THE INVENTION The present invention provides a method of increasing the efficiency of an epoxidation catalyst. Increased efficiency will reduce the consumption of raw materials and the production of waste materials to provide commercially acceptable bio-skins. It also allows the catalyst to be produced in a long period of time, so that the blood supply is very frequent. Preferably, the method of the present invention is carried out in a catalyst replacement process, which is carried out in the specific example of the secondary chemical device, whereby the present invention is in an emergency production time. During the start-up period, or substantially reduce the output, the light is turned into the light at 1 '0 inch' and does not ^ ^ ° to provide cost savings for specific specific examples. The efficiency of the agent: in the law, the invention provides - the kind of improvement Promoting epoxidation - and the bulk method comprises at a high temperature of at least about (10), or the gas phase epoxidation reaction promotes the feed of the sword = 5 ° CT, contacting the catalyst with a feed containing or having a duration of at least about 6 At least about 2 hours, at a time, preferably at least about 12 hours, or even 5 201041652 矸&gt;, about 24+ hours or longer. Then the temperature of the glow is made. Advantageously, during the high temperature period to two = equal to about 'or may promote if necessary Dimensions of different dimensions: = accelerator used in the epoxidation catalyst can result in a catalyst efficiency phase = = the catalyst efficiency before the increase is at least about 1%. Advantageously, the process of the invention can be carried out in situ, ie in the epoxy 2 During the startup or normal operation, the epoxidation can be set to = (4) with an increased life, so the catalyst replacement = slave can be extended and cost and time can be saved. In the second aspect, the present invention provides - An epoxidation of one or more agents: a method comprising contacting a catalytic epoxidation promoter, oxygen, and one or more rare hydrocarbon feeds at a temperature of at least about 24 rc, correcting at least about 2 Hour, or for at least about 6 hours, after = '12 hours, or even at least about 24 hours or longer. The temperature is less than or equal to about 眞. Advantageously, the accelerator, oxygen, or genus The degree may be maintained at the same time, or may be changed in one or more temperature stages as necessary. 实施 [Embodiment] The present invention may be further understood and/or illustrated when the following embodiments are considered together with the accompanying drawings. And so The features, aspects, and advantages of the present invention have been set forth in the specification. The present specification is intended to be a preferred embodiment of the invention. Importance or absence of this particular importance; rather, and unless otherwise stated, the terms will be understood by those skilled in the art in accordance with conventional usage. Unless otherwise defined, the technical and scientific terms used herein have familiarity with the subject matter. The meaning of the meaning of the epoxidation reaction is the same as that of the "efficiency" of the epoxidation reaction. Rate. The terms "efficiency" and "selectivity" are used interchangeably herein. The activity of the epoxidation reaction can be quantified in a number of ways' one way is the percentage of moles of olefin oxide contained in the outlet stream of the reactor relative to the inlet stream (the percentage of moles of olefin oxide in the inlet stream is typically (but Not necessarily) 〇%) while the reactor temperature remains substantially constant; and another way is the temperature required to maintain a given olefin oxide production rate. In many cases, the activity is determined over a period of time based on the percentage of moles of olefin oxide produced at a constant temperature. Alternatively, the activity can be measured as a function of the temperature required to maintain the olefin oxide which produces a molar percentage. The term "--", "second" and the like, as used herein, does not indicate Any order, quantity is important, and elements are distinguished from one another. In addition, the term "a" does not denote a limitation of quantity, and means that there is a reference to "in the case of ^" and unless otherwise stated, the terms "front", "back", "bottom" and / or "top" are used only for Convenient description, and no location or spatial orientation. If the scope is disclosed, all endpoints indicating the same 5" are included and can be independently combined, such as the range "up to about 25 wi%. 〇4 ft. 5 is about 5 wt.% to about 20 wt. /〇" includes the endpoints of the range "about $• /〇 to about 25 wt.%" and the 201041652 has: inter-value, etc.). Modifications in connection with the use of the <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; References throughout the specification to "a specific example", "an embodiment" or "an" And may or may not exist in other specific examples. In addition, it is to be understood that the described features of the invention may be combined in any suitable manner in various embodiments. The present invention provides a method for increasing the efficiency of ruthenium to promote an epoxidation catalyst. The method comprises contacting a catalyst with a feed comprising a gas phase epoxidation reaction promoter at a temperature of at least about 24 〇〇c. 2 hours, or at least about 6 days, or at least about 12 hours, or even at least about μ hours or longer' and then lowering the temperature to less than or equal to about the temperature of MC, advantageously, the method of the invention can be composed Typically used in the presence of an epoxidation process stream. For example, the feed stream can comprise - or a plurality of gas phase epoxidation reaction promoters, and the process of the invention can be carried out in the presence of - or a plurality of gas phase oxidation reaction promoters. It is believed that the gas phase epoxidation promoter can enhance the epoxidation catalyst by increasing the rate of the desired epoxy oxide and/or forming carbon dioxide and water relative to the formation of the desired epoxy compound to inhibit the formation of carbon dioxide and water. Efficiency and / or activity. Many of these accelerators are "and can be used in the method of the present invention. Blood qi.", type, gas phase promoters suitable for epoxidation reactions include organic compounds, and in detail include There are (4) compounds, 201041652 such as desertification or chloride. "Accelerator" is sometimes called "inhibitor", "modifier", "enhancer" or "moderator". Among these accelerators, chlorocarbons are particularly preferred. Suitable gaseous chlorine fumes include chlorocarbons having from 1 to 8 carbon atoms. Examples of such gas hydrocarbons include, but are not limited to, methyl chloride, ethyl chloride, dichloroethane, &amp; ethylene or any combination of such chlorocarbons. Particularly preferred gas phase epoxidation promoters for use in the process of the invention are ethyl chloride and dichloroethene. 0. Using a chlorocarbon gas phase promoter as an example, the ability of a salt enhancer to increase the process efficiency (e.g., efficiency and/or activity) of a desired epoxy burn depends on the gas phase promoter, for example, by The extent to which the catalyst surface is deposited, such as atomic chlorine or gas ions, is deposited on the catalyst. However, it is believed that smoke without chlorine atoms will strip chloride ions from the catalyst and thus detract from the overall increase provided by the gas phase promoter. A discussion of this phenomenon can be found in B^ty, Inhibitor Action of Chlorinated Hydrocarbons in the Oxidation of Ethylene to Ethylene Oxide, 5 Chemical 〇 Engineering C〇mmunicati〇ns Volume 82 (1) Machine Plus "Ethylene Coffee _", Appiied (5) her w , Volume 1 (1983), 2 () 7_238. Salt-like compounds such as Ethylene or Propylene are particularly effective for stripping gas ions from the catalyst. However, it is also believed that hydrocarbons such as ethylene and propionate will act to strip chloride ions from the catalyst. Some of these hydrocarbons may also be introduced into the Ethylene Feed as impurities or may be present for other reasons, such as for recycle streams. Typically, if present, the preferred concentration of ethane in the feed is from about 2 mole percent. If the gas phase promoter in the reactor feed stream has a competitive effect with the non-halogenated, non-promoting smoke 9 201041652, then the "〇verall halogenating effectiveness value" should be defined (in the case of organic chlorides) "Total gasification effect value (overaU chl〇riding also (10) (3) (4) value)") indicates the net effect of promoting and non-promoting gas phase substances in catalyst deuteration (or gasification). In the case of an organic chloride gas phase promoter, the total gasification effect can be defined as a dimensionless amount z* and is represented by the following formula: ζ· _chloroethane equivalent (1), wherein the gas ethane equivalent is The concentration of ethyl chloride in ppmv provides the same catalyst gasification effect as the organic gas chloride is present in the reactor feed stream at the concentration of the organic chloride in the feed stream; and the ethane equivalent is The ratio of the sulphuric acid to the sulphuric acid, which provides substantially the same degassing effect as the gas-free hydrocarbon in the feed stream of the gas-free hydrocarbon in the feed stream, and the right gas is burned in the reactor feed stream. The only gas phase chlorine-containing &amp; ethane equivalent is the concentration of ethane in ppmv. If the other contains a known agent (such as vinyl chloride, chloroform or digas), alone or! And the use of the hairpin I is the sum of the gas-fired equivalent of the chloroethane-concentrated bis-gas-containing gas promoter in ppmv (compared to the ethane by means of the second: correction). The relative effect of non-aerobic ethane promoters is the same as that required for the same process of ventilating and enthalpy and obtaining the chlorinated sulphur. As an additional step, if the desired dichloroethane content at the inlet of the reactor is 〇.5ppmV to achieve an equal effect depending on the catalyst performance provided by ippmv ethane, then for lppmv di- ethane The gas ethane equivalent is 2PPmv gas-fired. For hypothetical feeds with 丨ppmv di-gas bromide and i ppmv chloroethane, the ethyl chloride equivalent in the z* counter is 3 ppmv. As another example, it has been found that for a particular catalyst, the methane burn is only one tenth of the acetyl chloride effect. Therefore, for these catalysts, the methane equivalent of methyl chloride at a given concentration is 〇1χ (chloromethane concentration (in ppmv)). The amount of ethane s is the reactor feed stream. The ethane concentration in percent of the ear is added to the concentration of other hydrocarbons from the catalyst to effectively remove the gas ions (the relative effect of ethylene and ethane is corrected relative to the degassing effect of ethane by measuring the feed comprising ethylene and ethane The inlet ethyl chloride equivalent concentration providing the same degree of catalyst performance compared to the same feed having the same ethylene concentration rather than the specific ethyl chloride equivalent concentration and no ethane is experimentally measured. As a further illustration, if The composition of the material consisted of a concentration of 3 〇 () molar percentage ◎ and a concentration of 0.30 moles of ethylene. It was found that the 6.0 MPa methane equivalent level provided a similar but ethane-free feed composition. The catalyst performance of the same 3.0 ppm gas ethane equivalent is the same, then the 30.0 mole percent ethylene ethane equivalent is 〇3 〇 mole percentage. For the 30.0 mole percentage ethylene and 〇 3 mole percentage For the feed to the reactor of Ethylene, the ethane equivalent is a percentage of 06 moles. As another illustration, it has been found that for some catalysts, the degassing effect of methane is only 1/500 of ethane. Thus, for these catalysts, the ethane equivalent of methane is 0.002x (methane concentration (in moles per mole)). 201041652 for a typical example with a 30.0 mole percent ethyl and 〇1 molar percentage For inlet reactor feeds, the ethane equivalent is 〇4 mole percent. The relative effect of hydrocarbons other than ethylene and ethylene can be determined by measuring the feed containing the hydrocarbon of interest at its feed concentration. The inlet gas E-sinter Equivalent Concentration of the two different feedstocks at the E-steam concentration to achieve the same catalyst efficiency is measured experimentally. If the carbon ruthenium compound is found to have a very small degassing effect and is also present at a low concentration, then The contribution to the equivalent concentration of the hospital is negligible. - Therefore, the above relationship is known. In the case where the reactor feed stream includes ethylene, ethyl chloride, di-ethane, a ethylene and ethane, the total gas of the process is known. Effect value Defined by the following formula (II): (8) Z* a (〒CL + 2*EDC + VCL)

(c2h6+〇otc^hJ /, medium ECL, EDC &amp; VCL are respectively in the reactor feed stream in terms of PPmv ((4)(1), dichloroethane to C1-CH2-CH2_C1) (:2C = CH_C1) The concentration of coffee and C2H4 is the concentration of ethane and ethylene in the reactor feed stream with the molars + aa, &amp; Having =, those skilled in the art will recognize that while in the context of the present invention a single "gas" phase promoter can be utilized in contact with the catalyst under epoxidation conditions, a plurality of compounds can be formed, and thus the solution ^No. There are many compounds that can be used in the re-circulation loop. (4), will be relieved, even if the agent originally in the method of the present invention is still considered to be not only package 12 201041652 ', L includes any or all The reaction product formed during the application of the process. The concentration of the pore phase nucleation reaction promoter can be substantially preserved in the process. 5 $ can be changed ° advantageously 'and due to the total catalytic sword chlorination effect value 1 % Oxidation catalyst activity sometimes has an unwanted effect, In some specific examples of L month, at least during the treatment, the total catalyst gasification effect value is maintained at a substantially ambiguous level at a temperature of at least fine. In other specific examples of the invention, during the treatment, The temperature of the total catalyst chlorination may even decrease at a temperature of c or higher, :, at or equal to 250. _ The method utilizes a high temperature operation of a &amp; period during the initiation of the epoxidation process or the use of the catalyst to increase the ring. The efficiency of the oxidation catalyst. As used herein, the term "high temperature" means a temperature which is elevated relative to, for example, less than or equal to about 2 Torr. Ideally, from C, 25 〇〇Γ ^ &amp; The dish is at least about 24 〇 1 or as high as 250 ° C, or even higher. It has been found that the dimension n* pB ,, is only between the south temperature of the main 240 C, for example at least about 2 hours, or at least about 6 hours. , to an hour, or even at least about 24 hours or more, can provide, ^ tT Μ M ju ζ. * ', a significant efficiency improvement over the efficiency of other catalysts that initiate the process, such as at least about 〇 at least about 0.5% or Even at least about 1%. 5 It should be understood that Increasing the actual f may or may not be, even in the specific examples of the invention that can utilize one or more high temperature periods, to capture the cumulative effect on catalyst efficiency, the invention is provided herein. The ability to describe the results will be subject to at least the understanding of Yanhe, the rate limit. The theoretical maximum η catalyst efficiency for any given catalyst refers to the most favorable, 13 201041652 degrees, pressure, hourly gas space velocity and feed composition ( Package; optimal gas phase accelerator content) The highest efficiency of sputum smoke or oxygen conversion close to zero or concentration close to zero. It can be obtained, for example, by obtaining a curve of the efficiency versus epoxy concentration by changing the reaction temperature and then pushing the curve to zero epoxy concentration under the well-known inverse =: zero-epoxy burning The concentration extrapolation efficiency is regarded as the theoretical daring efficiency of the established catalyst. Two: temperature reduction 'ideally maintains the high temperature for a sufficient period of time to provide == Catalyst efficiency at least very small before the process of the invention is about 7 for example; about 〇·Ι%. High temperatures may ideally be maintained, for example, for about 2 hours, or even about 6 或 or 12 hours, or 24 hours, two hours, or 72 hours 'or 5 days, or... In particular, the present invention, which also carries out the method, is effective: "In the column, it is advantageous to utilize the most appropriate efficiency k, and the maintenance is better. % - about 2 hours to about 24 hours After the time required for high temperature, ideally lower relative to the separation, and By ^ ' dish degree may be in the specific example, the melon degree can be reduced to the required process operation - know, the required (four) 项 technology The operating temperature of the deuterated process typically varies: in some preferred embodiments, the temperature is lowered to 23 (TC or lower) after the high temperature. In the step, the temperature is generated by the control system. The library who ^ 』 artificial or borrower or both can be flat 4L solution 'temperature rise or fall - + π birth function or in the form of step function. Therefore 14 201041652 as The temperature fluctuations provided by the temperature (4)n, the specific temperature described herein includes at least the standard deviation associated with the measuring equipment and/or the temperature controller. The temperature value in the present invention refers to the gas phase temperature in the catalyst bed. Familiar with chemical processing technology It is known that the process temperature is typically indirectly measured. Further ❹ catalyzed direct measurement of the temperature of the sword bed can be obtained, for example, by operatively placing a thermocouple or fiber optic probe relative to the catalyst bed. Multiple 孰 couples can be used == needle In this case, τ' can be expressed using a weighted average based on the thermocouple/probe = distance in the bed. Alternatively, the average temperature can be obtained via mathematical integration of the temperature profile placed along the catalyst bed. The agent bed temperature can also be provided, for example, by combining the coolant temperature and the reaction calorimetric value and/or the calculated value, the measured value of the reactor effluent stream temperature, the prior knowledge of the system (the work data) and the mathematical model; Indirect quantities of the instantaneous estimation method of the wheel gallery, etc.: indirect or different. For the reactor using the water as the coolant, the temperature of the y can also be accurately calculated based on the steam waste measured in the reactor casing. Ease of use, many industrial epoxidation production facilities are profitable or calculated, and such values can be used in the method of the present invention, and the measured value of the outlet gas temperature is better. It is not critical to use the speculation technique, as long as The temperature is less than or equal to about _ (at least the package = dish | is at least about the job, and any expected temperature difference indirect measurement between the low and indirect measurement and the direct measurement). The exothermic nature of the epoxidation reaction 15 201041652, the average catalytic enthalpy (4).... The coolant temperature. The exact difference is seen in the reaction, the operating conditions and the catalyst performance. For example, = two!: catalyst (for example, And having boiling water as the coolant VA:: 'The average temperature in the catalyst bed is typically about 1 in the same temperature as the cold agent. It is widely known to those skilled in the chemical engineering industry that there are many suitable for (4) Method of reaction temperature in a chemical process, including but not limited to cold/dish, flow rate and pressure; reactor feed composition, space velocity and pressure f, and any of which can be used to adjust the process of the present invention The temperature. The process of the present invention can be used to increase the epoxidation catalyst efficiency during start-up or use or to reactivate a catalyst that has been used but has no effect due to a planned or unplanned kiosk. In other words, and surprisingly, the method of the present month allows catalyst efficiency of a feed gas towel that has been exposed or is being exposed to a desired reactant, such as one or more olefins L, relative to the catalyst efficiency prior to initiating the process. An effective increase of at least about 0.1 Å/〇^ can be particularly beneficial for the use of the catalyst of the invention comprising a catalyst for the epoxidation of olefins, and in particular for the epoxidation of olefinic or olefinic hydrocarbon mixtures. A number of references describe such reactions, and representative examples of such references are Liu et al., U.S. Patent No. 6,511,938 and Bhasin, U.S. Patent No. 5,057,481, and Kirk-Othmer Encyclopedia Chemical Technology, 4th Edition. (1994), Vol. 9, pp. 915-959, for all and all purposes, 'all references are hereby incorporated by reference in its entirety. Although the invention is not so limited, the application of the method of the invention will be further described in the light of the meaning of the invention and the use of a catalyst for epoxidation of ethylene. In general, the catalysts are supported catalysts and may comprise any of a number of known porous refractory structures or support materials as long as the chemistry of any selected luminescent refractory material used in the use of shaped porous bodies is utilized. Product and: Relatively inert in the presence of working conditions. It is also important that the carrier material

The rhodium and thus the catalyst based on such support materials are capable of withstanding substantial temperature and pressure fluctuations within the reactor. 'There are many well known methods for preparing carriers suitable for use in epoxy calcining catalysts. Some of the methods are described in, for example, U.S. Patent No. 4,379,m; No. 4, No. 518; No. 5, G63, 195; 帛 5,384, 3() No. 2, M31037, and the like. For example, a purity of at least 95%: the oxidation carrier can be prepared by compounding (mixing), extruding, drying, and high temperature forging. In this case, the starting materials usually comprise _ or a plurality of clay materials having different characteristics t 〇!-oxidized powder, which can be added as a binder to provide mechanical strength, and used in the form of a mixture after removal during the calcination step. A burnout material (usually an organic compound) that provides the desired porosity and/or pore size distribution. The level of impurities in the finished carrier is determined by the purity of the starting materials used and their volatility during the calcining step. Common impurities may include vermiculite, alkali metal and alkaline earth metal oxides, and trace metal and/or non-metal additives. Another method of preparing a support having properties particularly suitable for use in an alkylene oxide catalyst comprises mixing ceric acid with aluminate alumina (A100H) and/or y alumina as appropriate, with an acidic component and a tooth anion ( A mixture of preferred fluoride anions is used to peptize alumina to obtain a peptized halogenated 17 201041652 alumina, which is formed by, for example, extrusion or pressing, to form a peptized halogenated alumina to form a dried peptized alumina. The toothed alumina is obtained by forming a helmet water and oxidizing, and firing the anhydrous shaped oxide material to the a-alumina carrier pellet which is modified as appropriate. In one embodiment, the support material comprises at least about 8% by weight of alumina and comprises less than about 30 ppmw of acid leachable alkali metal, ... the weight percent of alumina and the concentration of acid leachable alkali metal as a carrier The weight of the acid leachable alkali metal is selected from the group consisting of lithium 'sodium, potassium, and mixtures thereof. The support material can be prepared to further comprise any other component necessary or desirable for processing, such as water, acid, binder, lubricant, dispersant, pore former, dopant, modifier, etc., such as (4) Office... (10)h ^ Principles of Ceramic Processing, J. Reedj WUey

These components are described in Interscience, (1988), which is incorporated herein by reference. The support material is desirably porous and has a measured surface area of at least about 〇5 m2/g (more preferably from about 77 m2/g to about 1 〇m2/g) and a measured pore volume of at least about 0.3 cc/ g (better about 44 cc/g to about 2 〇 cc/g) and a median pore size of from about 1 micron to about 50 microns. "Surface area" as used herein refers to the method by BET (Brunauer, Emmett, and Teller) as described in the J. urnal 〇f the American Chemical s〇ciety 6〇 (1938), pp. 3〇3 3i6. The surface area measured by nitrogen. "Total pore volume" means the pore volume of the support material and is typically determined by mercury porosimetry. "Porosity" is the ratio of the non-solid volume to the total volume of the material. Those skilled in the art can estimate the porosity by the total pore volume or water absorption as measured by mercury porosimetry 18 201041652. "Mesoporous pore size" means the pore diameter corresponding to the point at which the half total pore volume of the shaped porous body has been measured in the pore size distribution. The support material/catalyst can have any suitable shape as desired. Conventional industrial fixed bed ethylene oxide reactors are typically in the form of a plurality of parallel elongated tubes (in a suitable outer casing) having an outer diameter of from about 2 to about 7 and a length of from about 4 to about 14 meters. For use in such fixed bed reactors, the carrier (4) agent is desirably formed into a circle having a diameter of about (M pairs (0.25 cm) to about 8 nf dm), such as spheres, pellets, rings, tablets, and It has a similar shape. The epoxidation catalyst comprises, in addition to the support material, at least one catalytic species deposited thereon. Non-limiting examples of catalytic materials that may be advantageously supported by a support material include metals, solid compounds, molecular catalysts, enzymes, and combinations of such materials. The catalyst suitable for use in the epoxidation of ethylene typically utilizes silver as the catalytic material' and is preferred in the specific examples of the invention. Some conventional methods of initializing or improving the efficiency of the epoxidation catalyst require hydrazine to limit the amount of silver used in the catalyst. More specifically, and because some methods of W catalyst efficiency require a temperature greater than 25{rc and/or a reactive gas that can lead to silver contact sintering, for example, T / 7 / female can use The carrier material is silver of low concentration or density. Advantageously, the process of the present invention is not so limited, and the desired catalytic amount of silver can be used, i.e., any amount of silver that catalyzes the direct oxidation of, for example, ethylene to the corresponding alkylene oxide from oxygen or an oxygen-containing gas. Typically, the bulk material is greater than about 5 wt%, greater than about 1%, greater than about b 19 201041652 wt%, greater than about 2 by weight of the silver compound solution = chemical sufficient to provide silver on the support material. Immersion one or more times in an amount of 〇wt%, greater than about 25 wt%, preferably greater than about 27 Å: more preferably greater than about 30 wt%. Although the enthalpy of silver used is not specifically limited, the amount of silver provided in combination with the support material may generally be less than about 70% by weight, and more preferably less than about 50% by weight, based on the weight of the catalyst. In terms of density, the surface area of the catalytic material such as silver relative to the support material can be up to at least about 0.07 g/m2' or up to about 〇2 g/m2, or even up to about 0.3 g/m2 or higher. —·...This is another, the three targets are not narrow. Suitable silver particle size can range from about 1 〇 to about ι 〇, _ ang range: . Preferably, the silver particle size is in the range of greater than about _ angstrom to small (four) 5, ga. It is desirable that the silver be dispersed in a relatively uniform manner in the shaped porous body, in the entire shaped porous body, and/or on the shaped porous body. '^ = The catalysts desirably contain chains, and in some of them further include one or more other promoters that promote m^^^, 锞 promoted loading of silver-containing catalysis: from the United States: Patent No. 94 and US Patent No. No. 5 has been incorporated herein by reference in its entirety to the disclosure of the entire disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of An increase in the genus or a compound thereof and optionally, such as sulfur, hydrazine, boron, and a compound thereof. As is familiar to those skilled in the art, materials, which are useful in combination with a variety of known promoters of a particular catalytic material in the presence of catalyst-godo: (eg, silver), "4 multiple or additional promotions" The action of producing the desired product (e.g., an epoxidizing agent to be able to determine, and in spite of, the propylene propylene). More specifically, the promoters themselves are not considered to be catalyst materials 20 201041652. However, they typically promote one or more beneficial effects of the catalyst performance, to the rate or amount at which the desired product is produced, and the reduction is achieved. Properly react to the desired temperature, reduce the rate or amount of the reaction that is not normally required. Moreover, as will be appreciated by those of ordinary skill, the material that can act as a promoter for the desired reaction can be an inhibitor of another reaction. For the purposes of the present invention, an accelerator is a material that acts to a total reaction that is effective to produce the desired product, and whether or not it inhibits any competing reactions that may occur simultaneously. /, 〇 6 Known promoters for silver-based catalysts for epoxidized ethylene include, but are not limited to, bismuth, molybdenum, tungsten, lithium, sulfur, manganese, potassium, cesium, and cesium. The sputum, turn or crane may suitably be an oxyanion in the form of a salt or an acid, such as a perionate, a citrate or an antacid. Examples of accelerators, their properties, and methods of incorporating such promoters as part of a catalyst are described in U.S. Patent No. 5,187,14, to Th〇rsteins〇n et al., especially in the first; Uu et al. U.S. Patent No. 6,511,938; Ch〇u et al., U.S. Patent No. 5,5,4, 〇53; S〇° et al., U.S. Patent No. 5,1,2,848; Bhasin et al., U.S. Patent Nos. 4,916,243, 4,9,8,343 and 5, 〇59,481; and Launtzen, U.S. Patent Nos. 4,761,394, 4,766,1,5, 4,808,738, 4,820,675 and 4,833,261 All, for all and all purposes, all documents are incorporated herein by reference in its entirety to the extent that it can be in various forms, for example, in the form of a metal, in the form of a covalent compound, in a cationic form, or in an anionic form. The enthalpy of providing an increased efficiency and/or activity is uncertain&apos; and may be a component that is added during or during the preparation of the catalyst or during use as a catalyst. Examples of ruthenium compounds 21 201041652 include sulfonium salts such as hydrazine halides, 33-oxides, citrates, per-acid salts, cerium oxides and acids. However, it is also possible to use a metal permeate 夂 chain acid, a soil metal perrhenate, silver perrhenate, other per-alloys and antimony pentoxide. When ruthenium pentoxide RhO7 is dissolved in water, it is hydrolyzed to ruthenium or ruthenium hydrogenate. Therefore, for the second part of the specification, hepta tetroxide can be regarded as peroxylate, that is, (iv). Similar chemistries can be exhibited by other metals such as molybdenum and tungsten. Catalysts comprising silver as the catalytic material and at least as a promoter are expected to benefit in particular from the application of the invention, and such catalysts are preferred. In one particular embodiment, the catalyst may also desirably comprise a promoting amount of at least one other rhodium metal, and optionally a co-promoter. More specifically, it is selected from the group consisting of Group IA metals, lanthanum metals, molybdenum, tungsten, chromium, titanium, donor, erbium, vanadium, niobium, tantalum, niobium, tantalum, gallium and niobium and mixtures thereof. Preferably, the other metal is selected from the group consisting of Group IA metals such as clock, potassium, sodium, fine and fine, and/or Group IIA metals such as feed, record and lock. Its best for the clock 1 n / or planing. The amount of metal and ruthenium promoter can be determined in terms of total t (chain or metal) based on the total catalyst 〇 (H to · mmQl / kg1 selected Zhuang accelerators include (but not limited to) tungsten, fierce, molybdenum , chromium, sulfur 'scale, stone and a mixture thereof. The supported silver catalyst may comprise a ruthenium promoter, a first co-promoter and a second co-promoter; wherein the amount of the ruthenium promoter deposited on the support is relative to the catalyst The weight is greater than i _〇l / kg; wherein the first co-promoter is selected from the group consisting of sulfur, fill, butterfly and mixtures thereof; wherein the second co-promoter is selected from the group consisting of crane, indium, chromium and mixtures thereof and deposited on a carrier. The first co-promoter and the second co-promoter 22 201041652 The total amount of the catalyst relative to the catalyst may comprise a carrier and is deposited on the carrier. mmol/kg. The first co-promoter and the second co-promoter; The molar ratio of the cerium promoter and the co-promoter is greater than that of strontium, the co-promoter and the second phosphorus, boron and a mixture thereof; and the medium-accelerator is selected from the group consisting of sulfur, chromium and mixtures thereof. Package::::::: Department: (a), Ο ο: one and second co-promoter; its promoter More than 丨; Bean y Xingdiyi, Shi Peng "Gan', / /, the promoter is selected from the group consisting of sulfur, phosphorus, friends and mixtures; and the second co-promoter. Agent you, from tungsten, molybdenum, Chromium and its blends are included in the catalyst of the method of the present invention and any promoters required for it are ideally promoted in a quantity, a boat, a soil, and an ugly child. The amount of the accelerator that promotes the amount of one of the catalysts containing the accelerator is effectively improved by the catalyst of the specific accelerator. Examples of characteristics include, inter alia, resistance (resistance to runaway), selectivity, activity, rate. 彳ί e me The effects of the chemical, stability, and U-producing agents can be affected by many variables, such as Reaction conditions, catalyst preparation techniques, surface area and porous structure and surface chemistry of the support, silver and listener content of the catalyst, presence of other cations and anions on the catalyst, other activators, stabilizers, ::agents, enhancers or Other catalyst improvers The presence of the oxime also promotes the effect. An exemplary suitable amount of ruthenium is expected to be about 0.0001% (1 ppmw) i 2 weight percent (2 〇, deleted 23 201041652 ppmw) based on the total weight of the catalyst. Ppmw) to 5% by weight (5000 ppmw). When used, the amount of ruthenium component can generally be at least about 1 ppmw based on the total weight of the catalyst, such as at least about 5 ppmw' or between From about 1 ppmww to about 2000 ppmw, typically between about 20 ppmw and 1 〇〇〇 ppmw. Methods of preparing epoxidation catalysts are well known in the art, and any of these methods are suitable for preparation. The catalyst of the process of the invention is carried out. Generally, such methods include one or more impregnation steps with one or more solutions containing the desired catalyst component. Typically, the reduction step is performed during or after the impregnation to form metallic silver particles. The method of forming a catalyst is described, for example, by Thorsteinson et al., U.S. Patent No. 5,187,140, the disclosure of which is incorporated herein by reference. It has now surprisingly been found that an epoxidation catalyst can be reactivated or increased in efficiency by subjecting the catalyst to elevated temperatures in the presence of a gas phase % oxidation reaction promoter. Advantageously, the process of the present invention can be utilized in situ, i.e., during catalyst startup or operation, when the catalyst is in situ in the epoxidation processing facility without substantial fluctuations in the production of the desired alkylene oxide. The method of the present invention can increase the time interval between catalyst replacements, and thus significantly saves cost and time. Further cost savings can be achieved by increasing the efficiency of the catalyst and saving the form of the raw materials after applying the method. The process of the present invention may also result in a reduction in the production of by-product carbon dioxide, and thus the process of the present invention also provides environmental benefits. Accordingly, the present invention also provides a process for the epoxidation of an olefinic hydrocarbon. Those who are familiar with chemical engineering are familiar with these methods. An exemplary method is described in 24 201041652

In Kirk Othmer, Encyclopedia of Chemical Technology, 4th Edition, Vol. 9, 1994, pp. 925-939, and for any and all purposes, the contents of the paper are hereby incorporated by reference.

The 5' subsequent 'epoxidation reaction can be carried out in any suitable reaction, such as a fixed bed reactor, a continuous stirred tank reactor (CSTR), and a fluidized bed reactor, many of which are already familiar to the skilled artisan. It is well known and need not be described in detail herein. It is also desirable to recycle the unreacted feed, utilize a single pass system, or use a continuous reaction to increase ethylene conversion by using sequentially arranged reactors, which can be readily determined by those skilled in the art. The selected mode of operation is usually governed by process economics.

The oxime oxidation reaction is generally exothermic. Thus, a cooling system (e.g., a cooling jacket or a hydraulic circuit with a coolant, such as a heat transfer fluid or a water) can be provided at a temperature of the reactor. The heat transfer fluid can be any of a number of well known heat transfer fluids such as tetralin (1,2,3,4-tetrahydronaphthalene). In a reactor using boiling water and helium, a coolant in the form of liquid water is introduced into the cold side of the reactor, most commonly the shell side. When it flows through the cooling side, the heat is removed from the self-made side... some of the water is vaporized into steam. The coolant exits the cooled side of the reactor as a mixture of water and steam. The steam leaving the reactor is recirculated back to the coolant side population by removing heat from the heat. Refrigerant in the reactor

The temperature of the agent is determined by the boiling of water, 1 A, and the boiling point is controlled by its operating pressure.

Decide. The pressure is controlled by means of a pressure-operated exhaust valve that discharges the steam-water mixture from the cooling side of the reactor. The oil addition _ typically uses a closed loop controller to adjust the coolant temperature by automatically adjusting the venting to maintain the pressure necessary to maintain the desired temperature. 25 201041652 A olefin (olefinic hydrocarbon) (preferably ethylene) # is converted to an olefin oxide (preferably ethylene bromide), for example by about _. (: to about the time. (: the temperature and the required mass speed and the social &amp; productivity and 疋 between about 5 atmospheres (506 kPa) and about 30 atmospheres (3·〇Μρ〇, The feed stream containing rare earth J ethylene) and oxygen or an oxygen-containing gas and a gas phase promoter (parts per million) is continuously introduced into a reactor containing a catalyst. The milk can be such as air or pure. The oxygen-containing stream of oxygen or oxygen-enriched air is supplied to the reaction. The obtained epoxy form, preferably epoxy bake, is separated and recovered from the reaction product by a conventional method. Any olefinic hydrocarbon can be utilized in the °H method, and Examples of such olefinic hydrocarbons which are desirably epoxidized include, but are not limited to, 1,9-decadiene, iota, butyl diisomethane, propylene, ethylene or such olefinic hydrocarbons, and Preferably, the olefinic hydrocarbon comprises ethylene. The octagonal oxidation reaction is desirably carried out in the gas phase, wherein the package is required to be contacted with an epoxidized money agent. In the form of a solid material, X, more specifically, can be 'charged in the desired reactor. The catalyst in the packed bed The amount may be at least about at least; 0 kg? 戈约心... 〇, or about - to ~ ° ° 5% more emulsification reaction is carried out in a continuous process, and the method encompasses the method of causing the desired reactor typically It may be equipped with a heat exchange device to control the temperature of the reactor and/or the method within the catalyst bed. For example, two or more components may be optionally included, including, when expected, inert gases, saturated hydrocarbons, and the like. Recirculating feeds are expected to be particularly likely to be present in carbon dioxide because carbon dioxide is a by-product of many of the 26 201041652 epoxidation processes. In these specific examples, Encyclopedia of Chemical Techn〇i〇gy, 4th edition (10) 4 ), in the conventional manner described in vol. 9, p. 915, 959, to remove the h—h oxidation* in the recycle gas because the carbon oxide has an adverse effect on the catalyst performance, especially the activity. Nitrogen, argon, or mixtures thereof may be included. The heat in the reactor may be controlled using, for example, fusing and hydrocarbons and the oxygen concentration in the feed is high.

The method of oxidizing an olefin in a specific example comprises: feeding a reaction mixture comprising an olefin, a milk gas and carbon dioxide with a silver, a ruthenium promoter, a first co-promoter and a second co-promoting comprising a carrier and deposited on the carrier Catalyst contact; wherein the amount of carbon dioxide present in the reactor mixture is 3 mol% based on the total reaction mixture; the first co-promoter is selected from the group consisting of sulfur, scales, and the like, and the second The accelerator is selected from the group consisting of cranes, keys, complexes, and mixtures thereof. During operation, epoxidation and deer crying λ. The pressure at the inlet of the Yingyingyi may typically be less than 4000 kPa' or less than 3500 kPa, $, U a or preferably less than about 2500 kPa absolute pressure' and in most cases at least勹王〆 1000 kPa absolute pressure. Gas space velocity per hour ("GHSV" A庐"; horse standard state temperature and pressure (Ot, 1 atm) per hour through a 箪彳 兴 „ y volume! The early volume of the gas filled in the catalyst bed. Preferably, in the specific example in which the epoxidation and the reaction are carried out in a rolling phase, the GHSV for starting the pb r self-twisting on the packed catalyst bed is desirably from about 2000 to about loooo per hour. The method of the present invention can be carried out as follows during the operation. A specific example at any time between the epoxidation process during start-up or operation, when the temperature is lower than 27 201041652, about 250 ° C, preferably less than ^1 9 j Λ -, about 240 C and the catalyst efficiency is ideal. When the ground is increased, the operating temperature is increased to at least about and up to about 25 generations, for at least about 2 hours, at least about 6 hours, at least about 匕 hours, at least about 24 hours 'about 48 hours', about 72 hours, or 5 hours. Days, or even i weeks. After the required time period, the temperature is, for example, reduced to 2 m: or lower than 23 〇t, and preferably falls to the temperature required for the desired epoxy plant production speed (iv). * At 40 C or 240 During the high temperature above C, the feed composition can be Substantially unchanged. More specifically, during high temperature, the reactor inlet oxygen concentration may desirably remain substantially constant 'eg, about 8 mole percent, and the reactor inlet lean smoke concentration may ideally remain substantially absent. For example, about 30 mole%, the inlet carbon dioxide concentration can also remain substantially unchanged, for example about 3 mole%, and the total catalytic (four) rms value can be kept constant on the real f, and # represents, for example, about 3 Alternatively, the feed composition may vary during 24 (TC or 24 (high temperature above TC: to maintain the desired level of epoxy burn during the application of the method of the invention. More specifically, when utilizing the method with Catalysis that has been used: At the time of the South Temperature period, the reactor inlet oxygen roll can be reduced, for example, to - about 1 mole %, or about 2 mole % or even about 3 mole %, as long as it remains safe. The operating conditions and the amount of alkylene oxide required to be - ^ * 4,1 ^ , the concentration of carbon monoxide is advantageously increased by at least about 0.5 mol %, or about 丨夭 / 〇, in the case of grass, the increase is affected by Design limitations for epoxidation processes. Total catalyst chloranil RMS Advantageously, for example, at least about 0.5 戋, 00 ϋ or more Ζ* is early, and in some cases the reduction is controlled by the process, and the olefinic hydrocarbon concentration can be substantially The maintenance is not quite good, the age can be at the same time at high temperature 28 201041652 . Drop:, 5 or 10 or even 15 mol%. In some of the inventions, the 'feeding component' should be adjusted during the temperature period. Only one of the inputs = degrees. In other specific (four) 'can change the two of the feed components or the production: death: 疋 combination to substantially maintain the required level of epoxy at high temperatures, every case When the adjustment of the composition of the feed gas is performed simultaneously with the operation of the next one, it is preferred to: return to substantially its previous level when operating down, or return to = 〇 to provide the desired level of epoxy The other concentration combinations of the amounts produced. Another example of the epoxidation process in which the process of the present invention is applied during the production can be carried out as follows. At any time during startup or operation, when the catalyst efficiency has decreased to a poor level, such as ^ i# s K I . When operating at lower efficiencies, the degree of dishing is increased to at least about 2 hours, at least about 6 hours, at least about 12 hours, at least about 24 hours, or even = price hours. Treatment can be carried out until the desired catalyst efficiency has been achieved, or until the catalyst efficiency is at least slightly increased. The feed composition can be maintained at a real k during a dish of 24 〇C or 240C; t;, ,® such as pq κ* .. 〇 i. Alternatively, the concentration of the milk and olefinic hydrocarbons may be lowered, for example, the oxygen concentration of the feed group = may be reduced from about 8 mol% to about 2 mol%, and the degree a may be reduced from 0 mol% to about 20 mol%. . In these specific examples, the concentration of agricultural carbon monoxide is about 3 mol%. And the total catalyst chlorination rms value may be slightly reduced, for example, expressed as Μ from about 3 to about 2, if changed during the heat treatment, the feed returns to its original composition as the temperature decreases. The main t-zone can be easily understood by those skilled in the art, and the epoxidation process 29 201041652 can be adjusted to achieve other examples of the desired epoxy plant production rate during high temperature and/or low temperature, reactor pressure and/or The space velocity can be varied or changed along with the inlet feed composition rather than the population feed composition to achieve a particular production rate at a particular operating temperature. The alkylene oxide produced by the epoxidation process of the present invention is typically processable to provide other downstream products such as 1,2-diol, glycol ethers, ! 2_ Carbonic acid vinegar and alkanolamine. Since the present invention provides an improved epoxidation process, the improvements provided are intended to be modified to improve such downstream processes and/or products. Therefore, an improved process for producing &amp; glycols, &amp; glycol ethers and alkanolamines is also provided herein. The % oxygenate is converted to hydrazine, and the second to the second (tetra) may comprise, for example, suitably reacting the desired alkylene oxide with water in the presence of an acidic or basic catalyst. For example, for the bis-diol which is preferentially produced over 1,2-diol ether, the alkylene oxide may be present in the presence of, for example, 0.5 to 0% by weight of a sulfuric acid catalyst based on the total reaction mixture. At about 50 ° C to about 70 ° C in a liquid phase reaction at 1 bar absolute pressure, or at about 13 (TC to about 24 (rc and about 2 bar to about 4 bar absolute pressure, preferably no In the presence of a catalyst, it reacts with ten times moles of water in a gas phase reaction. If the proportion of water is lowered, the proportion of hydrazine and 2-diol ether in the reaction mixture will increase. The resulting hydrazine, 2-diol The ether may comprise a diether, a triether, a tetraether or other polyether. Instead of the 1,2-diol ether it may be prepared by converting the alkylene oxide with an alcohol such as methanol or ethanol, or by replacing at least a portion of the water with an alcohol. The resulting 1,2-diols and di-alcohols can be used in a variety of end-use applications in industries such as food, beverages, tobacco, cosmetics, thermoplastic polymers, curable resin systems, detergents, heat transfer systems, etc. 30 201041652 Conversion of the alkylene oxide produced by the process of the invention to an alkanolamine can comprise, for example, reacting the alkylene oxide with ammonia Should be used anhydrous ammonia or ammonia, but anhydrous ammonia is advantageous for the production of monoalkanolamines and can be used when monoalkanolamines are preferred. Known klk amines can be used, for example, in the treatment of natural gas. The 2-carbonate is converted by reaction of an olefin oxide with carbon dioxide. If desired, the 1,2-diol can be prepared by subsequently reacting "2-carbonate with water or an alcohol to form a diol. For a suitable method, reference is made to US Pat. No. 6,897, the entire disclosure of which is hereby incorporated by reference in its entirety in its entirety in the the the the the The method of the present invention is utilized during the soil oxidation process to increase the efficiency of the catalyst: the use of the crucible to promote the efficiency of the catalyst. The density relative to the carrier is in the range of (four) grams per square meter. More preferably, the epoxidation process will be carried out in a CSTR reactor. , 〇 electric couple direct measurement temperature eCSTR ^ = enthalpy in the catalyst basket is basically Λ &amp; phase so that the temperature in the catalyst bed process has fallen within 15 ° C. At the beginning of this method, epoxy 86% Day, the temperature is about 23Gt and reminder The efficiency of the agent was stable at about the end of the 15th day, and the operating temperature was increased to about 2 days. The temperature was then reduced to about the same time, and the skin was kept for 1 day. Finally, the temperature was lowered to 23. At a slightly lower skin temperature = holding feed composition, also... oxygen concentration approx. concentration of about 30 mol% b Wudou/〇 inlet ethylene. and inlet carbon dioxide concentration of about 3 mol%. Target into 31 201041652 The Ethylene burn concentration was maintained at G.5 mol%, and the total catalyst gasification RMS value was initially about 1.3 Z*, but was adjusted to about i9z after the first day of the second day, when the catalyst was near steady state operation. The compensating activity is gradually decreasing. The results of this example are shown in Figures 1 and 2. In summary, and as shown in the figure! It is shown that after returning to the operating temperature of 23 (rc, the catalyst efficiency will increase to about 87%, and the improvement is about one percentage point. During the efficiency increase/activation at 25 〇 and 240 ° C, the catalyst remains operational and produces Ethylene oxide (EO). As shown in Figure 1, the efficiency decreased during 25 (rc, but then returned to about the original value at 240 ° C. As shown in Figure 2, the EO production rate increased during activation. The original value, but surprisingly returns substantially to the original value when the temperature drops to 230 ° C. That is, there is substantially no yield loss during activation. Example 2 and Comparative Example 3 These examples are illustrated in terms of A specific example of the method of the present invention during the initial startup period - the effect of operating the catalyst at a temperature of 240 ° C or higher, before the temperature is lowered to 23 Torr or lower. The same Re- used as in Example 1 Two unused 40 cc samples of the promoted silver catalyst batch were loaded into the CSTR reactor as used in Example 1 and started using the following reaction conditions: the target inlet feed composition was 8 mol% oxygen, 30 mo Ear % Ethylene ' 3 mol % carbon dioxide, 5 mol % Ethylene bromide, 2 ppmv chloroethene; reactor pressure 2000 kPa absolute pressure (275 psig); total flow rate is 320 standard liters per hour (11.3 scfh) per nitrogen. For Example 2 'reaction The temperature of the reactor was set to 240 ° C, and for Comparative Example 3, the reactor temperature was set to 23 (TC. The temperature of each embodiment 32 is shown in Figure 3. The profile is maintained as shown in the figure. The first seven days of each operation. During this period, the target inlet ethyl chloride concentration was changed in parallel to determine the reaction of the catalyst to the inlet total catalyst chlorination RMS (Z*). The inlet total catalyst chlorination of each example was effective. The value (Z*) characteristics are shown in Figure 4. After Day 7, for the operation of Example 2 and Comparative Example 3, the cumulative yield was 0.035 and 0.031 kT EO per cubic meter of catalyst, respectively. 2.2 and 1.9 Mlb EO) For the 8th day, the reactor temperature for the operation of Example 2 was 240. (: decreased to 230 ° C. As shown in Table 1 below 'between the 9th and 13th days, at Under the condition of substantially consistent, when the target inlet ethyl chloride concentration is flat When changing, the two reactors were operated to study the Z* reaction. When the operation of Example 2 was as low as the catalyst productivity obtained by measuring the concentration of ethylene oxide in the outlet stream of the reactor, 'on the same day' The efficiency exceeded the operation of Comparative Example 3 by more than one percentage point. These examples thus show that the application of one of the methods of the present invention during startup can increase catalyst efficiency relative to conventional methods. Table 1 Days Example 2 Comparative Example 3 T(°〇Z* EO% Efficiency% T(°C) Z* E0% Efficiency% 9 230 1.89 1.42 87.1 230 1.86 1.56 85.3 10 230 1.42 1.35 87.2 230 1.43 1.48 85.7 11 230 1.48 1.36 87.0 230 1.54 1.48 85.5 — 12 230 1.51 1.39 86.9 230 1.50 1.48 85.5 13 230 1.27 1.31 86.9 230 1.24 1.40 85.7 — 33 201041652 Some of the features of the present invention are illustrated and described herein, but many modifications and changes will occur to those skilled in the art. The above embodiment further describes the present invention without limiting its van. It is to be understood that the appended claims are intended to cover all such modifications and . BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph showing the % efficiency of a cyclizing agent which has been subjected to the process of the present invention in an epoxidation process; Figure 2 is a period before and during the process in which the catalyst used in the epoxidation process is subjected to the process of the present invention. And thereafter, an epoxy epoxide production pattern of the epoxidation process; FIG. 3 is a diagram of an embodiment of the present invention and a temperature wheel used in a comparative example according to a conventional method; 4 is a diagrammatic view of an embodiment of a comparative embodiment performed in accordance with one embodiment of the present invention and a comparison of embodiments according to conventional methods. [Main component symbol description] None 34

Claims (1)

201041652 VII. Scope of application for patents: * !·--In-situ increase chain promotes 瑷 ^ Φ , and the rate of emulsifying catalysts in operation is at least about 24 含. (: The method of making 嗲 ν 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰 丰And, and then the temperature is 2. Further included in the scope of the patent application - or a plurality of other promoters, including: oxidation catalyst planer, strontium, magnesium, calcium, strontium, barium, gas, lithium, sodium, potassium,铷, 虱, sulphur, manganese, bismuth, molybdenum; 5 〇 3. For the method of claim 2, the order, steel, and tungsten. The accelerator includes planer. #T by- or a variety of other 4·such as applying for a patent The accelerator of the scope of the third aspect comprises an organic toothing. The method, wherein, the gas phase epoxidation inverse 5 is as described in claim 4 of the scope of the invention. The method wherein the organic toothed package comprises 6. A method for epoxidizing one or more olefinic cigarettes, at a high temperature of 2401, to promote a ruthenium ring, ruthenium 3 at least about ◎ should promote ruthenium, oxygen, and p ruthenium (tetra) ruthenium and contain gas phase epoxidation counter...: or various women Contact with hydrocarbon feeds, lasting at least about 2 hours' and then this time And further reduced to a low temperature of less than or equal to about 23 Gt. /., as claimed in the patent scope of the 6th olefin. The method, wherein the olefinic hydrocarbon comprises B. As claimed in the scope of the invention 6 ^, ^ ^ α 备 η &lt; The method of the gas phase promoter, the oxygen wind and one or more of the olefinic Q ^ ^ genus remain the same at the temperature and low temperature. 9. If the patent application Fan Tu Chu &amp; agent, oxygen and / Or - (4): a method in which the concentration of at least one of the gas phase promoting sub-multiple species is different at a high temperature of 35 201041652 and a low temperature. 10. - Manufacturing 1.2 - ^ , ' s, 1, 2 - a solution of di-ether ether, 1,2-acidic amine, which comprises detective &amp; ^ 奴 知 or alkanol 乳 乳 转化 转化 , , , , , , , , , , , , , , , , , , , Alkanolamine, hydrazine, - a solution of ether, method to prepare, the ring t (four): oxidized genus of ancient hydrocarbons (7) table 侑 虱 虱 虱 虱 虱 虱 包含 包含 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少 至少Promoting the epoxidation catalyst to contact with a feed comprising a gas phase epoxidation reaction promoting oxygen, oxygen and one or more olefinic hydrocarbons for at least about 2 hours And then the temperature was reduced to less than or equal to about 23 (rc of the low eight, FIG formula: (summarized as follows p) 36